SA519410415B1 - A catalyst for producing olefin having enhanced stability, conversion rate and selectivity, and a preparation method thereof - Google Patents

Abstract

The present invention is to provide the catalyst for producing olefin having enhanced stability, conversion rate and selectivity, and a preparation method thereof. The catalyst for producing the olefin of the present invention comprises a support including an alumina and a sub-support component, and a catalytic component comprising a metal component and an alkali metal impregnated on the support. Fig 2

Description

A CATALYST FOR PRODUCING OLEFIN HAVING ENHANCED STABILITY, CONVERSION RATE AND SELECTIVITY, AND A PREPARATION METHOD THEREOF FULL DESCRIPTION BACKGROUND The invention Jal relates to a catalyst catalyst to produce olefin 016170 with enhanced stability, conversion rate and selectivity; and method of preparation. Olefin such as ethylene (plug lly ethylene) is widely used in the petrochemical field Olefin can generally be produced from the naphtha thermal cracking process, but due to the increasing demand for olefin more and more in the petrochemical field, there is an attempt For the production of olefin from low-grade hydrocarbon by the catalytic dehydrogenation process 01005.00 for example propylene (plug ll (JU) is a basic material Lac used as an indicator in the field of petrochemicals such as ethylene ©60//A607 It can be converted into many chemical compounds because it contains a methyl group and an allyl group in the form of “Lis.” It is used to a large extent in the production of polypropylene, which is used in plastic plastics. thermoplastic plastic Uj and also used as raw material in acrylonitrile 15, propylene oxide (pb ll), epoxy resin, oxo alcohol, 55:31 isopropyl alcohol, etc. Until now; Propylene is mainly produced as a byproduct of the crude oil cracking process, or it is produced with ethylene by steam cracking of gall

38 which is obtained from the distillation of crude oil. However, due to the focus of Ula technology in ethylene production on the cost-saving decomposition process, which makes it difficult to increase the size of the halal ball process, the source of proylene supply is limited. And recently, the global demand, especially in China and India, for propylene used in vehicles and electrical material has increased rapidly, which leads to an increase in the imbalance between supply and demand with regard to

in propylene. Accordingly, tailor-made saving technology has become a major problem to solve the aforementioned problem. specifically; Much research is currently being done on the 4- to 8-carbon olefin conversion process and olefin metathesis

process 0, digas process, methanol to propylene, broyan dehydrogenation, etc. In the aforementioned processes, ole dehydrogenation of broyan has received a lot of attention lately due to the price advantage of converting propylene to propane and the increasing demand for the development of environmentally friendly energy production technology. The cost of broyan decreases due to the rapid development of shale gas and oil, especially in North America, which leads to the expectation of strengthening the ability to reduce the costs associated with it.

5 “The broyan dehydrogenation techniques currently in use are based on a noble metal catalyst and a discontinuous process. Although a continuous process; it is recognized that it is not suitable for mass production of many millions of tons of propylene due to a problem in the operation of the catalyst bed. In addition, the broyan dehydrogenation reaction has a thermokinetic-limited conversion rate due to the hydrogen-induced reverse reaction.

0 problem; Many processes use an external oxidizer (Jie oxygen), halogen 07, sulfur compound, carbon dioxide, steam, etc. to convert hydrogen into water. Therefore, there is a demand to develop a new process for dehydrogenation of propane while reducing production costs by solving the continuous process problem and using a low-cost non-noble metal catalyst in order to efficiently produce large quantities of propylene.

In the case of the noble metal catalyst among the catalysts used for the dehydrogenation of propane (lg ll) the reaction takes place according to the direct dehydrogenation mechanism where the hydrogen is adsorbed to the active site. However, in the case of transition metal oxide it is not possible Clearly verifying the mechanism due to the instability of the active site due to the movement of electrons .electron .mobility 5

in a transition metal catalyst; The catalyst in which chromium oxide or vanadium oxide is impregnated on alumina is used as active phase phase 8017/6. There is an attempt to imbibe a small amount of an alkali metal at the same time in some catalysts to prevent the generation of a by-product due to the location of the acid in the alumina support.

support 00108 Nala. However, it is not possible to obtain a sufficient yield of propylene with the said metal only because of the side reaction and therefore, from a realistic point of view, research is required to find a more effective catalyst. lg on it; The authors of the present invention (ASE) disclosed in prior art (Korean Patent No. 0651418 and Korean Patent Publication No. 2017-0007636) have been searching continuously

5 And the development of a catalyst for the production of an olefin with an excellent degree of stability, conversion rate and selectivity at the same time and the method of its preparation. The difference between the present invention and the prior art

The invention Mall | S|Rokicki Allison | Zimmerman (Reference 1( | (Reference 2) (Reference 3)

active metal | essential | Mineral components: | chromium group chromium (phase) chromium; vanadium; eighth: manganese; iron ; Platinum Coil 4 Palladium or Molybdenum Clad is a mixture of them Zinc; Cerium and sub-nickel | Alkaline metal zirconium There is no zirconium chtem also includes a and also includes silica alkali metal and /  lanthanime  or alkaline earth metal alkali metal and mixture and the group thereof dae al third and / or fourth (deb) Subsub | zirconium»; Zinc No, Zirconia No, and Platinum by comparison to Reference 2 cited; Allison [0040] during the ODH reaction; The oxidized feedstock includes an oxidant capable of oxidizing at least gia of the hydrocrionic feedstock. However ; The present invention relates to the direct dehydrogenation of a saturated hydrocarbon using an oxidant; which differs from the ODH reaction

So ; Alison is not appropriate as a reference to quote from. Comparing Ref. 1 and 3; As shown in the table above; The semi-active metal zirconium and rockiki mainly comprise zirconium. However ; The semi-active metal of the present invention does not include zirconium. He did not mention in Zimmerman and Rokiki the sub-support component. GENERAL DESCRIPTION OF THE INVENTION The purpose of the present invention is to provide a catalyst for olefin production with enhanced stability, conversion rate, and selectivity; And the way to prepare it. The purpose of the present invention is to provide a catalyst for olefin production comprising an alumina-containing support, a ¢sub—support component, and a catalytic component 0 comprising a metal component and an alkali metal. impregnated on the abutment. The support subcomponent shall comprise any chosen element among zirconium 21000010017, zinc 60, and platinum The support subcomponent is preferably zirconium having a molar fraction of 0.01 to 0.1 for aluminum in alumina (Zr : Al) 5 may be The metallic component of any chosen element from among chromium oxide, vanadium, manganese 6, iron, iron, cobalt, molybdenum, copper, copper, zinc, cerium, and nickel. and 9620 wt. of catalyst. It is preferred that the alkali metal be potassium, which ranges between 0.5 and 962.0 by weight of catalyst 0. It is also preferable that the surface area of the catalyst ranges between 80 and 300 m2/g and that the pH of alumina does not exceed µmol/13lm 2.0.5.

An embodiment AT of the present invention provides a method for preparing a catalyst (Jalal) for olefin production which includes providing a support comprising a sub-support component and alumina and preparing a pre-catalyst by impregnating and calcining a metal component oxide on the support; A component metal oxide and an alkali metal oxide are impregnated into the pre-catalyst and calcined. In dlls the catalyst for olefin production of the present invention; The conversion rate and selectivity are impressive

The degree of stability with respect to the satisfactory life of the catalyst is excellent (Wiad), which makes the degree of efficiency (J) economically distinct from a commercial perspective. Brief explanation of the drawings FIG. 1 is a graph describing the broyan conversion rate of the Gy catalyst for the comparative metal

0 and the present invention. Figure 2 is a graph describing the broyan selectivity of the catalyst according to the comparative metallurgy and the present invention. Figure 3 Ble of a graph describing the carbon balance of the comparative Jill ay catalyst and the present invention.

5 Figure 4 is a graph describing the conversion rate after hydrothermal treatment Gg for the comparative example and the case of zirconium support impregnation at the same time. Figure 5 is an Aly graph describing the selectivity after hydrothermal treatment according to the comparative example and the simultaneous zirconium support impregnation condition. Detailed description:

0 The present invention provides a catalyst for the production of an olefin comprising an alumina-containing support and a sub-support component; and a catalytic component comprising a metal component and an alkali metal impregnated on the support.

Preferred examples given in the present invention will be described hereunder with reference to the accompanying figures. It is understood, however, that these examples can be modified in various ways and that they are not to be construed as limiting the scope of the present invention. The By catalyst of the present invention comprises a support and a catalytic component.

The support includes an alumina and a sub-support component and the catalytic component impregnated onto the support is a metallic component and an alkali component. The sub-support component includes any element or combination of zirconium, zinc, and platinum. Preferably the support sub-component is zirconium which exists with a molar fraction of 0.01 to 0.1 relative to aluminum in alumina (ZA).

0 The durability of the catalyst (of Jad's invention) is enhanced by the sub-brace component. The function of catalyzing the CH bond in the paraffin raw material is more Baar than using only alumina as a support. As a result, the hydrocarbon conversion rate and olefin yield are superior, with enhanced olefin selectivity. In the form (als), zirconium plays a role in enhancing the durability of the alumina support. When the amount of the sub-support component, especially zirconium, is less than 0.01 of the molar ratio

5 for aluminium; The characteristic effect of enhancing durability is not achieved. In the presence of more than 1 the impregnated metal component and the alkali metal cannot be jointly dispersed due to the rapid decrease in the surface area of the alumina support. The metallic constituent may be any chosen element among oxides of chromium, vanadium, manganese, iron, cobalt, molybdenum, copper, zinc, serbium, and nickel. It is preferable that the metallic component be represented by:

Chromium, which ranges between 10 and 9620 by weight of the catalyst. When the amount of the metallic component, especially chromium; less than 1610 wt.; The active site of the catalyst is very small in the chromium phase. when having a FST of 9620 by weight;

The main active phase in chromium can be reduced due to the interaction between the metal and the support and the excess metal-binding strength. Therefore an ideal load within the said range is required. It is preferred that the alkali metal be potassium; Which ranges between 0.5 and 960.2 by weight of the catalyst, which leads to the possibility of controlling the acidity of the alumina by not more than 0.5 micromol 2eNH3 / when the amount of alkali metal 0, especially potassium, is less than 0.5% an “sil”. For not controlling the acid site of the alumina support, a side reaction of acid decomposition is carried out, which leads to the generation of coke in excess, and the lack of control over the active phase of chromium, which reduces the yield to 0. When an iS of 2% by weight is present ; The potassium subcomponent reduces the pores of the alumina preventing mass transfer 0 for catalytic activation during contact with the reactant. The alumina support preferably includes sh 7-0 at a preparation temperature of 550 to 850 degrees above the dehydrogenation temperature and with a surface area of 80 to 300 m2/g within this range. When the support is prepared at a temperature lower than the dehydrogenation reaction temperature, 5 thermal deformations of the catalyst can occur during the dehydrogenation reaction. when preparing at a temperature above 850 degrees; The surface area of the catalyst is reduced due to crystallization of the support, which prevents mass transfer of catalytic activation during contact with the reactant. Another embodiment of the present invention provides a catalyst preparation method for olefin production 0 016080 which includes provision of a support comprising a sub-support component and alumina and preparation of a pre-catalyst by impregnation of a metal component oxide on the support, calcining and dipping of a metal component oxide SH and alkali metal oxide in the pre-catalyst and its calcination. Despite the method of preparation described above; Those skilled in the art will recognize the possibility of several changes and modifications which are within the scope of the present invention.

— 0 1 — The present invention will be described in greater detail using examples and preparation examples. Ja Preparation > 1. Support preparation (Zr-Al203) 8 Catapal (alumina sold by Sasol) is stirred 13.89 kg added to 25 kg water for 30 minutes and 1.83 kg ZIO is mixed (NO3)2 and 25 kg of

water and stir also for 2.5 hours. It was then sprayed dry (feeding speed 0.56 g/min; Jara 6000 per million atomizer, inlet temperature 208 degrees, outlet temperature 125 degrees) and separated by sieve (sieve: 75 to 200) and calcined at 650 degrees for 6 hours.

2. Catalyst preparation [Cr+0.5%K)/5%Cr/Zr-Al203%35)] Mix 0.482 g of CrO3 and 2. 5 g of water, impregnation with aad from dale all prepared above, drying at 120° and calcination at 700° for 3 hours (pre-catalyst). 0.482 g of CrO3, 8 g of KNO3, and 2.5 g of water are mixed and impregnated with 5 g of Cr/Zr-Al203%5 prepared above, dried at 120 degrees, and calcined at 700

5 °C for 3 hours le leads to the preparation of the catalyst provided for in the present invention. Lav Experiment for conversion rate and selectivity > To check the conversion rate and selectivity of the prepared catalyst Gy of the present invention; The GC (FID, TCD) is analyzed in a catalyst-charged fixed-bed flow-through reactor maintained at a vacuum velocity of 8400 mL/g .081 h at 600° and atmospheric pressure. is described

The results of the experiment are shown in Figures 1 to 3. As shown in Figures 1 and 2; When the catalyst provided in the present invention was impregnated with the metallic component and the alkali metal (potassium: (K) at the same time, the conversion rate discreteness was verified

— 1 1 —

and eclecticism. In addition to that; As shown in Figure 3; The generation of and coke resulting from the side reaction Sin in the catalyst provided for in the present invention was Carbon Balance a> 4. Stability Experiment >

To verify the hydrothermal stability of the prepared catalyst By of the present invention; In the case of adding the subsupport component (zirconium: (ZF) to the alumina support of the catalyst according to the present invention and the other case in which the subsupport component was not added to the catalyst (comparative example); the conversion rate and selectivity were measured in the same way as above after Treat the catalyst at 100°C and 96100° steam for 24 hours (Figs. 4 and 5).

0 as shown in Figures 4 and 5; In Alla the addition of the sub-support component (zirconium: (Zr dale) alumina of the catalyst Gy of the present invention”; the excellent hydrothermal stability was investigated. Preferred examples presented on the present invention are described in detail above. While Those skilled in the art will recognize that the scope of the present invention claimed is not limited to these examples and that

Ke 5 introduces several changes and modifications that are within the scope of the present invention. Industrial Applicability The present invention relates to a catalyst with enhanced degree of stability, conversion rate, and selectivity for olefin production and method for its preparation.

Claims (1)

Claims 1 ly catalyst lea olefin consisting of: an alumina-containing support and sub-support component 0000001; and a catalytic component comprising a metal component sl and an alkali metal impregnated on the support 5 wherein the metal component gall is a metal oxide selected from the group consisting of chromium and vanadium manganese, iron, iron, cobalt, molybdenum, copper, copper, zinc, cerium-7, nickel, and Cus-terminated mixtures. The surface area of the catalyst ranges between 80 and 300 m 2 / 0 g, and the pH of alumina should not exceed micromol NH3 / m 2. 2. Gg catalyst for claim 1 where sub-support component 500-50000011 is selected from czirconium, zinc, platinum 07. 3. The catalyst according to claim 2 wherein the sub— support component is zirconium having a molar fraction of 0.01 to 0.1 with respect to aluminum in alumina (Zr : Al). 0 4. The catalyst according to claim 1; Where the metal component is chromium, which is between 10 and 9620 by weight of the catalyst. 5. catalyst By of claim 1; Where is where the alkali metal is potassium 001855017 which is between 0.5 to 72.0 by weight of the catalyst .catalyst 25 — 3 1 — 6. The method for preparing a dg catalyst for claim 1 includes: providing a support comprising a SUb—sUppOrt component and alumina; Preparing the pre-catalyst by dripping a metal component oxide into the support and calcining it; And dripping a metal component oxide and an alkali metal oxide in the pre-catalyst and calcining it 9 m, where the manufactured catalyst is the catalyst a, catalyst for protection element 1. 0 7. Method Gg for protection element 6 where the sub-support component is chosen from zirconium, zine and platinum 8. Method according to claim 7 wherein the component of sub-support 071 is zirconium ZIFCONIUM having a molar fraction of 0.01 to 5 0.1 for aluminum in alumina (Zr: Al) 9. Method “Gig for claim 6” wherein the alkali metal is chromium 0070 which is 10 to 20 by weight of 7 catalyst 0 10. Method according to claim 6” wherein the alkali metal is metal is potassium, which is 0.5 to 2.0 wt 7 of the catalyst —_ 1 4 —_ 1 Figure RE D Br ANE : ve. Lt | AG (ee AR Brighten Fe gir Ya vod Se i wd CE Fuwa Jum RAY Br dy . ِ ْ : EBT Dr ÷ Fr ner BI en 4 800 Yr : º | 1 | : 2 : +} : º : | :: ir. * ? 0 | ْ ْ, :: : No. — 1 5 — Figure ? : ; ; BBs rg: . :: : “a Caw '8 8 1 * 1 : ® Be > and Nae ¥ av A LAE 8 oF Lo & : : } - : me a te te te. af Te we that | Dany Oy ent Rhee Fy Arey x £ 5 A oe XY 6 A weight I-85 + Figure 86 #?rrr a a. Ce All Rd ARR : » # { : : i * : i i : i ° * | :: | Aaa Aaa, except that Aaa Aaa 76 A: Ski: 0 sn:: Cel Orde Jr Mut: 8: 8: 8 34: CB Fer but «Orie 0 ¥ * 2 ::: . A A: a ْ: a kut CRD He A De Er Attar BLY «dd te oo to: T.E. CRT Oe RA Ke Br ner Bs gerbe br erp « X £ 3 A B L Yi 5 Ga 1-0-8 Fig. BY AA AA AA AA C B : º : CRY Or AA ow : L A: Pr A Bhd L A A Bhd «Bele red Done 2 + | | . Aa Jho Fr Al 3 An « mn ne UX + Aem Zr An * Asl 4 A y ْ : : - ot + : : khok Fr Al Rs for the following Because Wx Be Rhee ST : ® ْ: * + + ْ: : + + + + : Wx BY % someones Fr Be 0: : ! ] : Pra ws we Bo Aha : ¥ § % & ve 8 y y {any T-0-5 8 a Figure 4 Ys EE EE BY + 4 2 y+?1+” b ++> My jelly. EE TRCN CE for Joe we BWC eh Fr ANYY ~ amr Tr wa deer fe fe * ¥ £4 & a # + * reply 1-0-5 The Saudi Authority for Intellectual Property Sweden Authority for Intellectual Property pW RE .¥ + \ A 0 § Um 5 + < Ne ge “Benaj > Aye Ki Jada Li Days TEE Bbha Nase eg + Ed - 2 - 3 .++ .* provided that the annual financial fee is paid for the patent and that it is not null and void due to its violation of any of the provisions of the patent system, layout designs of integrated circuits, plant varieties and industrial designs or its implementing regulations. »> Issued by + BB 0.B Saudi Authority for Intellectual Property > > > “+ PO Box 1011 .| for ria 1*1 uo ; Kingdom | Arabic | For Saudi Arabia, SAIP@SAIP.GOV.SA